Solid epoxy resins from hydrogenated bisphenols and aromatic dicarboxylic acids

ABSTRACT

Solid epoxy resins are prepared from diglycidyl ethers of a hydrogenated bisphenol such as hydrogenated bisphenol A and a dicarboxylic acid such as isophthalic acid. These solid resins may be comminuted into a stable free-flowing powder useful as epoxy resin powder coatings having excellent weathering properties.

United States Patent 11 1 1111 3,864,316

Robinson 1 Feb. 4, 1975 SOLID EPOXY RESINS FROM [56] References Cited HYDROGENATED BISPHENOLS AND UNITED STATES PATENTS AROMATIC DICARBOXYUC ACIDS 3,523,143 8/1970 Kwong 260/835 75 Inventor; G|enn Clarke Robinson Lake 3,551,517 12/1970 Dowbenko... 260/834 Jackson, Tex. 3,555,111 1/1971 Benham 260/830 [73] Assignee: The Dow Chemical Company, OTHER PUBLICATIONS Midland, Mich, Chem. Abst., Vol. 67, 1967, p. 22429g.

[22] Filed: 1974 Primary ExaminerMelvin Goldstein 21 APPL 440,413 Assistant ExaminerT. Pertilla Related U Application Data Attorney, Agent, or Firm-James G. Carter [63] Continuation-impart of Ser. No. 366,389, June 4, [57] ABSTRACT 1973' Solid epoxy resins are prepared from diglycidyl ethers of a hydrogenated bisphenol such as hydrogenated bis- [52m UISI minim/78.4 EP, henol A and a dicarboxylic acid such as isophthalic [51] hm CL Cosg 30/00 (368g 30/10 acid. These solid resins may be comminuted into a sta- Field 4 EP 75EP 830 TN ble free-flow ng powder useful asepoxy resin powder 266/835 2 coatmgs having excellent weathering properties.

26 Claims, N0 Drawings SOLID EPOXY RESINS FROM HYDROGENATED BISPHENOLS AND AROMATIC DICARBOXYLIC ACIDS This application is a continuation-in-part of my previous application Ser. No. 366,389, filed June 4, 1973.

This invention relates to epoxy resins and more particularly it relates to epoxy resins which are useful as powder coatings for outdoor service.

Higher molecular weight epoxy resins suitable for powder coatings usually have a Durrans softening point of from about 80 to about 120C and above and have usually been prepared form glycidyl ethers of bisphenols and bisphenols. However, such resins possess poor weathering characteristics.

A copending application Ser. No. 366,390, filed June 4, 1973, which is a continuation-in-part of application Ser. No. 229,181, filed Feb. 24, 1972 now abandoned, discloses epoxy resins prepared from glycidyl ethers of hydrogenated polyhydroxy aromatic compounds and aromatic or cycloaliphatic dicarboxylic acids which possess excellent weathering characteristics.

It has now been unexpectedly discovered that the epoxy resin compositions ofthe present invention have excellent weathering characteristics and improved physical properties and are suitable for use in epoxy powder coating compositions.

The novel epoxy resin compositions of the present invention comprises a solid product having a softening point above about 80C and preferably from about 90 to about 120C and which can be comminuted to a free-flowing stable powder which results from the reaction of a diglycidyl ether of a hydrogenated'bisphenol or polyglycidyl ether ofa hydrogenated novolae having an average functionality of from about 2.01 to about 2.6, preferably from about 2.01 to about 2.3, and (a) from about to about 25 percent, preferably from about 18 percent to about 22 percent by weight (based upon the total weight of reactants) of an aromatic or cycloaliphatic dicarboxylic acid and (b) from about 1 percent to about 10 percent, preferably from about 2 percent to about 4 percent by weight (based upon the total weight of reactants) of an aliphatic dicarboxylic acid having from about 4 to about 10 carbon atoms or the acid terminated adducts of an aromatic or cycloaliphatic dicarboxylic acid or anhydride thereof with an aliphatic dihydroxyl containing compound represented by the general formulas wherein R is independently hydrogen, methyl ethyl, chloromethyl, bromomethyl or iodomethyl, .r has a value of from 1 to about 3, preferably from 1 to 2 and v has a value of from 3 to about 10, preferably from about 3 to about 4; wherein the quantities of the glycidyl ether and the dibasic acid or said adduct is such as to provide an epoxyzCOOH ratio of from about 1.1:] to about 2.0:], preferably from about 1.111 to about 1.8:1, and most preferably from about 1.3:1 to about 1.5:1.

The term free-flowing stable powder used herein means that the epoxy resin when ground or otherwise comminuted into a free flowing powder will remain free flowing for at least 48 hours.

The novel epoxy resin compositions of the present invention are readily prepared by reacting a diglycidyl ether of a hydrogenated bisphenol or hydrogenated novolac with an aromatic or cycloaliphatic dibasic acid at a temperature of from about to about 210C in the presence of a suitable catalyst such as tertiary amines, quaternary ammonium compounds, quaternary phosphonium compounds. or the like, for a time sufficient to produce the product, usually from about 0.5 to about 30 hours. It is usually desirable, particularly when laboratory apparatus is employed, to preblend all of the reactants and then add the catalyst thereto.

Suitable catalysts include, for example, quaternary ammonium compounds such as benzyl trimethyl ammonium chloride, amines such as N-methylmorpholine and phosphonium compounds such as those compounds disclosed in US. Pat. No. 3,477,990 and Canadian Pat. No. 893,191.

Suitable glycidyl ethers of a hydrogenated bisphenol include the glycidyl ethers of such hydrogenated bisphenols such as, for example, hydrogenated p,p'- isopropylidine-diphenol, hydrogenated p,pmethylenediphenol, hydrogenated dihydroxydiphenyl sulfone, hydrogenated 4,4-dihydroxy biphenyl, hydrogenated 4,4-dihydroxydiphenyloxide, mixtures thereof and the like.

Suitable hydrogenated polyglycidyl ethers of novolac resins include, for example, those represented by the formula wherein R is independently hydrogen or an alkyl group having from 1 to about 4 carbon atoms, each X is independently hydrogen, chlorine, bromine or an alkyl group having from 1 to about 4 carbon atoms and n has an average value of from about 1.01 to about 1.6, preferably from about 1.01 to about 1.3.

Suitable aromatic carboxylic dibasic acids include phthalic acid, terephthalic acid, isophthalic acid, and those acids represented by the formula wherein Z is independently selected from a divalent hydrocarbon group having from 1 to 6 carbon atoms,

such as, for example, 4,4'-diphenylsulfide dicarboxylic acid, 4,4-diphenyldisulfide dicarboxylic acid, 2,5- furan dicarboxylic acid, 4,4-diphenyloxide dicarboxylic acid and mixtures thereof.

Suitable cycloaliphatic dibasic acids include, for example, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexyltetrahydrophthalic acid, dimethylhexahydrophthalic acid, methylhexahydrophthalic acid, hexylhexahydrophthalic acid, bromotetrahydrophthalic acid, chlorotetrahydroisophthalic acid, chloren- 4 employed andgtheparticular catalyst or curing agent depends upon the properties desired as those skilled in the epoxy resin art arereadily aware. Those not so skilled in this art but who desire to make use of this indic acid, methyltetrahydroterephthalic acid, mixtures vention are directed to the Handbook of Epoxy Resin. thereof and the like. Lee and Neville, McGraw Hill Book Co.. 1967.

Suitable aliphatic dicarboxylic acidsinclude. for ex- Although the novel epoxy resins ofthe present invenample, adipic acid, succinic acid, suberic acid. sebacic tion are particularly useful in epoxy resin powder coatacid, mixtures thereof and the like. ing formulations they may also be employed in molding Suitable acid terminated adducts of aliphatic dihycompositions, admixed with suitable solvents for use 111 droxyl containing compounds with aromatic or cycloalsolution coatings, castmgs, potting compounds, adheiphatic dicarboxylic acids or anhydrides thereof insives and the like. elude, for example, adducts of tetrahydrophthalic an- The following examples are illustrative of the present hydride with ethylene glycol, tetrahydrophthalic anhyinvention but are not to be construed as to l1m1tmg the dride with diethylene glycol, tetrahydrophthalic anhyl5 scope thereof in any manner. I dride with l,4-butanediol, phthalic anhydride with propylene glycol, isophthalic anhydride with dipropyl- EXAMPLES ene glycol, mixtures thereof and the like. I H

in the preparation of the solid epoxy resins of the I a Series f l s, epoxy resins were prepared present invention, the quantities of hydrogenated dib ddi to a tio v l equipped with a means glycidyl ether of a bisphenol-or novolac and mixture of f r i i temperature control, and nitrogen purge, a an aromatic or cycloaliphatic dicarboxylic acid and aliprebiended mixture of a ether of hydroge. phatic dicarboxylic acid or adduct of an aromatic or cy- Hated bisphenol A EHB having an average cloaliphatic dicarboxylic acid an aliphatic are xide equivalent weight of about an aromatic Such as to Prbvlde the resultant Solid p y resin with carboxylic acid or mixture of an aromatic dicarboxylic a percent cpoxide of from about 2 to about 6 n pr facid and an aliphatic dicarboxylic acid or adduct of a ra ly om abOUt 3 I0 about 4 and a Durfans Softening cycloaliphatic or aromatic dicarboxylic acid anhydride P of at least about with an aliphatic dihydroxyl-containing compound. The hovel p y resin Compositions of the Present The temperature was raised to 100C and N-methyl invention y be Cured to a thermoset Product y y 30 morpholine (NMM) was added as a catalyst. Heating 0f the know" catalysis of Curing agents Such as P was then continued to about ll50C and then alary. ndary an t a y am n s. a d d lowed to exotherm to a temperature of about 170C. hydrides and the e. The reaction mixture was then digested for about l-3 The quantities of curing agent or catalysts employ d hours at a temperature of about 150C. The reactants depends upon the particular catalyst or curing agent 35 and results are given in the following Table I.

TABLE I COMPONENTS Example 1 Example Example Example Example 5 Example Example Example Example AND PROPERTIES (Comparative) 2 3 4 (Comparative) 6 7 8 9 DGEHBA, grams 231.6 193.3 332 210 211 190 312 312 312 Aromatic Acid:

type/grams A'/68.4 A/53.9 A/87.7 A/45.l A/29.3 A/53.9 A/77 A/79 A/79 Aromatic A id" 22.8 21.56 20.42 16 .7 I087 21.57 19.37 19.75 19.74 Aliphatic Acid:

type/grams 0 3 /28 B/9.8 B/l5 B/29.3 5/6 C"'/8.5 D"/9 E/9.2 '71 Aliphatic Acid" 0 1.12 2.28 5.55 10.87 2.4 2.14 2.25 2.3 NMM, grams 0.23 0.2 0.33 0.2 0.2 0.2 0.3 0.3 0.3 7: Aliphatic Acid based on total wt. of Acid 0 4.94 10.05 24.96 10.02 9.94 10.23 10.43 Durrans Softening 84 83 87 87 gelled in I02 87 84 Point, C reaction vessel 72 Epoxide 3.8 3.7 3.6 3.1 ND." 3.5 3.11 3.21

COMPONENTS AND PROPERTIES Example 10 Example ll Example l2 DGEHBA. grams 305 304 304.2 Aromatic Acid:

type/grams A/76 A/76.6 A/76.6 7t Aromatic Acid 23.45 l9.l6 19.15 Adduct:

type/grams F"/l9.l (jll 9.2 H/l9.2 /r Adduct" 5.119 4.11 4.11 NMM. grams 0.3 0.3 0.3 /l Adduct based on total wt.

of acid adduct 20.08 20.04 20.04 Durran's Softening Point, C 83 85 83 7t Epoxide 3.3 3.2 3.4

' Aromatic Acid A was isophthalic acid. Aliphatic Acid 8 was adipic acid.

Aliphatic Acid C was succinic acid.

Aliphatic Acid D was suberic acid.

5 ND. not determined.

Adduct F was prepared from tctruhydrophthalic anhydride and ethylene glycol in a molar ratio of 2:] respectively. 7 Adduct G was prepared from tctrahydrophthalic anhydride and diethylene glycol in a molar ratio of 2:l respectively. Adduct H was prepared from tetrahydrophlhalic anhydride and l,4-butanediol in a molar ratio of 2:] respectively.

" /1 based upon total weight of reactants. Aliphatic acid E was sebu cic acid.

EXAMPLES 13-23 Each of the Examples l-4 and 6-]2 were formulated into a powder coating on a roll mill and electrostatically sprayed onto cold rolled steel panels. The

and (B), of an aromatic dicarboxylic acid or cycloaliphatic dicarboxylic acid and 2. from about 1 to about 10 percent by weight.

1 based upon the total weight of components (A) MOD-A-FLOW is a flow control agent commercially available from Monsanto Co.

TABLE III Days Exposure I: Reflectance 0 (initial) 78 I6 82 34 87 o 87 84 88 lt is clearly evident from the above data that the atmosphere does not adversely affect the gloss of the coating.

I claim:

1. A solid epoxy resin having a Durrans softening point of at least 80C which can be comminuted into a stable, free-flowing powder prepared by reacting A. an epoxy resin selected from 1. a diglycidyl ether of a hydrogenated bisphenol and 2. a polyglycidyl ether of a hydrogenated novolac having a functionality of from about 2.01 to about 2.6, or

3. mixtures thereof; with B. a mixture consisting of 1. from about 10 to about percent by weight,

based upon the total weight of components (A) coated panels were then baked in an oven at 175C for 5 and 0 30 minutes. The coating formulation and results are allphatlc dlcarboxyllc acld hill/mg from 4 given in the following Table ll. Although the ratio of about 10 carbon atoms 1 the quantity f curing agent l d. t quantity f b. an acld termmated adduct of an aromatic or epoxy resin is different, each quantity of curing agent, cycloallphatlc dlcarboxyllc acld or anhydride trimellitic anhydride (TMA), is percent of stoichiowith an liph i dihydroxyl Containing commetric. pound represented by the general formulas "a- TKELE. .M. 2-.

Example 13 Example Example Example 7 Example Example Example Example COMPONENT (COMPARA- 14 15 I6 17 I8 19 20 TlVE) Resin, from Example No./grams l/200 2/200 3/250 4/200 6/200 7/200 8/200 9/200 TMA. grams 23v 23 28.1 20 14 22 24 24 Tio 146 149 186 146 145 148 148 I48 MOD-A-FLOW* 1.8 1.8 2 1.8 1.8 1.9 1.9 1.9 Gardner Reverse Impact,

in-lbs. 10-10 30-30 -100 -120 10-20 30-40 60-80 60-80 Coating Thickness, mils 1.2-1.7 1.3-1.5 1.5 1.6 1.7-1.5 1.3-1.5 1.3-1.5 1.3-1.5

Example Example Example COMPONENT 21 22 23 Resin. from Example N0./grams l0/262 l l/262 12/262 TMA, grams 27 27% 27 Tio 192 192 192 MOD-A-FLOW* 1.3 1.3 1.3 Gardner Reverse Impact,

in-lbs. 60 50-60 60-80 Coating Thickness, mils. 1.5 L5 [.5

HOfCHrfiH-O}?! and HO(CH });OH

'whei' efii e acli li is independently hydrogen, methyl, ethyl, chloromethyl, bromomethyl or iodomethyl, x has a value of from I to about 3 and y has a value of from 3 to about 10, or 0. mixtures thereof; wherein the quantities of components (A) and (B) are such as to provide the resultant solid epoxy resin with a percent epoxide of from about 2 to about 6 and a softening point of at least 80C.

2. The solid epoxy resin of claim 1 wherein component (A) is a diglycidyl ether ofa hydrogenated bisphenol and component (B1) is an aromatic dicarboxylic acid.

3. The solid epoxy resin of claim 2 wherein percent epoxide is from about 3 to about 4.

4. The epoxy resin of claim 3 wherein component (A) is the digylcidyl ether of hydrogenated bisphenol A.

5. The epoxy resin of claim 3 wherein component (B1) is isophthalic acid and component (B2) is adipic acid, succinic acid, suberic acid or sebacic acid.

6. The epoxy resin of claim 5 wherein component (A) is the diglycidyl ether of hydrogenated bisphenol A.

7. The epoxy resin of claim 3 wherein component (Bl) is isophthalic acid and component (B2) is an acid terminated adduct of tetrahydrophthalic anhydride with ethylene glycol, diethylene glycol or 1.4- butanediol.

8. The epoxy resin of claim 7 wherein component (A) is the diglycidyl ether of hydrogenated bisphenol A.

9. A thermosettable composition comprising an epoxy resin of claim 3 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.

10. A thermosettable composition comprising an epoxy resin of claim 4 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.

11. A thermosettable composition comprising an epoxy resin of claim 5 and a catalytic amount ofa curing catalyst or a curing amount of a curing agent.

12. A thermosettable composition comprising an epoxy resin of claim 6 and a catalytic amount ofa curing catalyst or a curing amount of a curing agent.

13. A thermosettable composition comprising an epoxy resin of claim 7 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.

14. A thermosettable composition comprising an epoxy resin of claim 8 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.

26. The cured composition of claim 14.

composition of claim composition of claim composition of claim composition of claim composition of claim of claim 9.

of claim 10.

of claim 11. of claim 12. 

1. A COLID EPOXY RESIN HAVING A DURRAN''S SOFTENING POINT OF AT LEAST 80*C WHICH CAN BE COMMINUTED INTO A STABLE, FREEFLOWING POWDER PREPARED BY REACTING A. AN EPOXY RESIN SELECTED FROM
 1. A DIGLYCIDYL ETHER OF A HOMOGENATED BISPHENOL AND
 1. FROM ABOUT 10 TO ABOUT 25 PERCENT BY WEIGHT, BASED UPON THE TOTAL WEIGHT OF COMPONENTS (A) AND (B), OF AN AROMATIC DICARBOXYLIC ACID OR CYCLOALIHPATIC DICARBOXYLIC ACID AND
 2. FROM ABOUT 1 TO ABOUT 10 PERCENT BY WEIGHT, BASED UPON THE TOTAL WEIGHT OF COMPONENTS (A) AND (B), OF A. AN ALIPHATIC DICARBOXYLIC ACID HAVING FROM 4 TO ABOUT 10 CARBON ATOMS, B. AN ACID TERMINATED ADDUCT OF AN AROMATIC OR CYCLOALIPHATIC DICARBOXYLIC ACID OR ANHYDRIDE WITH AN ALIPHATIC DIHYDROXYL CONTAINING COMPOUND REPRESENTED BY THE GENERAL FORMULAS
 2. a polyglycidyl ether of a hydrogenated novolac having a functionality of from about 2.01 to about 2.6, or
 2. A POLYGLYCIDYL ETHER OF A HYDROGENATED NOVOLAC HAVING A FUNCTIONALITY OF FROM ABOUT 2.01 TO ABOUT 2.6, OR
 2. from about 1 to about 10 percent by weight, based upon the total weight of components (A) and (B), of a. an aliphatic dicarboxylic acid having from 4 to about 10 carbon atoms, b. an acid terminated adduct of an aromatic or cycloaliphatic dicarboxylic acid or anhydride with an aliphatic dihydroxyl containing compound represented by the general formulas
 2. The solid epoxy resin of claim 1 wherein component (A) is a diglycidyl ether of a hydrogenated bisphenol and component (B1) is an aromatic dicarboxylic acid.
 3. The solid epoxy resin of claim 2 wherein percent epoxide is from about 3 to about
 4. 3. MIXTURES THEREOF; WITH B. A MIXTURE CONSISTING OF
 3. mixtures thereof; with B. a mixture consisting of
 4. The epoxy resin of claim 3 wherein component (A) is the digylcidyl ether of hydrogenated bisphenol A.
 5. The epoxy resin of claim 3 wherein component (B1) is isophthalic acid and component (B2) is adipic acid, succinic acid, suberic acid or sebacic acid.
 6. The epoxy resin of claim 5 wherein component (A) is the diglycidyl ether of hydrogenated bisphenol A.
 7. The epoxy resin of claim 3 wherein component (B1) is isophthalic acid and component (B2) is an acid terminated adduct of tetrahydrophthalic anhydride with ethylene glycol, diethylene glycol or 1,4-butanediol.
 8. The epoxy resin of claim 7 wherein component (A) is the diglycidyl ether of hydrogenated bisphenol A.
 9. A thermosettable composition comprising an epoxy resin of claim 3 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.
 10. A thermosettable composition comprising an epoxy resin of claim 4 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.
 11. A thermosettable composition comprising an epoxy resin of claim 5 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.
 12. A thermosettable composition comprising an epoxy resin of claim 6 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.
 13. A thermosettable composition comprising an epoxy resin of claim 7 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.
 14. A thermosettable composition comprising an epoxy resin of claim 8 and a catalytic amount of a curing catalyst or a curing amount of a curing agent.
 15. An article coated with the composition of claim
 9. 16. An article coated with the composition of claim
 10. 17. An article coated with the composition of claim
 11. 18. An article coated with the composition of claim
 12. 19. An article coated with the composition of claim
 13. 20. An article coated with the composition of claim
 14. 21. The cured composition of claim
 9. 22. The cured composition of claim
 10. 23. The cured composition of claim
 11. 24. The cured composition of claim
 12. 25. The cured composition of claim
 13. 26. The cured composition of claim
 14. 